Monocyclic carbocyclic aromatic amine



MQNOCYCLEC CARBGCYCLIC ARUMATIC AMlNE Hans Eohler, Rheinfelden, FritzKehrer, Basel, and Piero Maderni, Binuingen, Switzerland, assignors toSandoz Ltd, Basel, Switzerland, a Swiss time No Drawing. Filed July 21,1959, er. No. 828,469 Claims priority, application witzerland, July 29,1958,

62,362, amendments thereto, Nov. 28, 1958, Mar. 24,

195%; July 9, 1959, 75,538 1 13 Claims. (Cl. 260-279) This inventionrelates to a process for the production of pigment dyestufis of thequinacridine-7,l4-dione series, which consists in reacting 1 mole of a2,5-dihalogenoterephthalic acid or one of its esters eithersimultaneously or successively with 2 moles of an aromatic amine or of amixture of different aromatic amines, in which at least one positionortho to the amino group is free, and con verting the resulting2,5-diarylaminoterephthalic acid or its ester into aquinacridine-7,14-dione by heating at a high temperature in an acidcondensation medium, if desired in presence of an inert organic solvent.

In the process disclosed herein the 2,5-dihalogenoterephthalic acid orits ester is condensed with the aromatic amine or amines in a polarsolvent or a mixture of polar solvents such as water, low molecularalcohols, glycerine, ethylene glycol, propylene glycol, polyethyleneglycol or water-ethylene glycol mixtures or water-glycerine mixturesetc. in presence of metallic copper or a copper compound and of asuitable acid-binding agent in the pH region of 2 to 12, preferablybetween pH 4 and pH 9, and at temperatures above 70 C., e.g. between 70and 160 C.

Condensation can be carried out in one step, but it is preferablyconducted in two steps'using in the second step the same amine or adifferent amine or a mixture of amines.

Examples of suitable amines are aminobenzene, 2-, 3- and 4-methyl-,-methoxy-, -chloroand -nitro-1-aminobenzenes, theamino-dimethyl-benzenes, amino-methylchloro-benzenes,amino-methyl-methoxybenzenes, aminornethoxy chlorobenzenes,amino-methylnitrobenzene, amino methoxy nitrobenzenes,amino-chloro-nitrobenzenes, amino-dinitrobenzenes, amino-dichloroandaminotrichlorobenzenes.

Suitable copper compounds are, e.g., cupric acetate, chloride, sulfate,oxide or hydroxide, cuprous oxide and cuprous chloride, and organiccopper salts such as copper octoate, copper benzoate or the copper saltof 2,5-dihalogenoterephthalic acid, while the preferred metallic copperis Raney copper. It is advisable to employ only a small amount of thecopper salt or Raney copper, e.g. 1 to on the weight of the2,S-dihalogenoterephthalic acid. However, an equimolecular amount of thecopper compound may also be used. a

Of the acid-binding agents of interest for the process, the followingmay be cited: sodium and potassium carbonate, bicarbonate and acetate,monosodium, monopotassium, disodium and dipotassium phosphate, borax oran excess of the aromatic amine or amines employed. The acid-bindingagent is added before the start of the reaction, or insmall portionsduring the course of the reaction in solid, finely powdered form or insolution. In the latter case a solution of sodium or potassium hydroxidecan also be used as acid-binding agents. A suificient amount of theagent is added to bring the pH of the reac tion mixture within thedesired limits.

One mode of operation of the process which is of particular interestconsists in boiling with reflux the copper salt of the2,S-dihalogenoterephthalic acid with an excess of one of theabove-defined amines in water in presence of an acid-binding agent suchas sodium or potassium United States Patent acetate, and separating thecondensation product by acidification with hydrochloric acid. Thereaction mixture, which depending upon the conditions chosen may bedirected to contain predominantly mono-condensation products, e.g.2-chloro-S-arylaminoterephthalic acid, or dicondensation products, e.g.2,5-diarylaminoterephthalic acid, is separated by dissolving the rawproduct in dilute sodium hydroxide solution followed by fractionalprecipitation with acid. With decreasing pH value the reaction prodnetsare obtained as technically pure compounds in the order2,5-diarylaminoterephthalic acid, 2-chloro-5-ary1- aminoterephthalicacid and 2,5-dichloroterephthalic acid. The2-chloro-5-arylaminoterephthalic acid is condensed in the describedmanner, e.g. in ethylene glycol, preferably at temperatures above C.,with a further molecule of an aromatic amine, which may be the same asor different from that used in the first step of the condensation, oralternatively a mixture of amines.

The hitherto unknown asymmetric and symmetric 2,5-diarylamino-terephthalic acids produced by the above described processare crystalline compounds of red to violet color. The2-halogeno-5-arylaminoterephthalic acids, which have been but littledescribed in the literature and are in great part unknown, aresubstances of yellow to orange color.

The main lines of the process as described above can be varied inaccordance with the character of the chosen amine and the desired degreeof monoor dicondensation. The possibility of choosing the desired degreeof condensation is a special advantage of the process, since it permitsthe operation to be carried through monocondensation to a secondcondensation giving new and hitherto unknown asymmetric2,5-diarylaminoterephthalic acids, e.g.Z-phenylamino-S-(nitroarylamino)-terephthalic acid, and by ring closureof the latter to arrive at the hitherto unknown quinacridones of theprocess, e.g. mononitroquinacridone.

The ring closure to give the quinacridone is accomplished by heating the2,S-diarylaminoterephthalic acid or its ester at temperatures above C.with an acid condensation agent, e.g. phosphate pentoxide, boric acid,60-85% sulfuric acid, 50-85% borosulfuric acid, but preferablypolyphosphoric acid or more than 75% P 0 content, and if desired inpresence of an inert organic solvent, e.g. cymene, dichlorobenzene ornitrobenzene. By working with polyphosphoric acid in the temperaturerange to 250 C., the quinacridine-7,14-dione can often be obtained innearly quantitative yield.

A special advantage of this ring closure process using polyphosphoricacid is that diarylaminoterephthalic acid esters, which can be producedby the process described by H. Liebermann in the Annalen der Chemie 404,272 (1914), are also convertible into the appropriate quinacridones inexcellent yield without previous saponification.

A special mode of operation of the polyphosphoric acid process consistsin mixing the diarylaminoterephthalic acid with an excess of P 0 andcarefully adding water so that a solution of not less than 75% P 0 isformed, this then being heated at 160 C. The quinacridone so formed isisolated by the addition of water and if necessary purified bydissolving in a solution of dimethylsulfoxide and alcoholic potassiumhydroxide followed by filtration and subsequent precipitation of thefiltrate with Water.

As is evident from U.S. Patents 2,844,484, 2,844,485 and 2,844,581, theunsubstituted linear quinacridone (quinacridine-7,14-dione) firstsynthesized by H. Libermann and described in the Annalen 518, 245(1935), can be obtained in an ot-, ,6- or 'y-crystal phase.

A further advantage of the polyphosphoric acid process for theproduction of quinacridones is that, after ring closure, thequinacridone or its derivative is present in solution in the acid andcan be directly converted by suitable precipitation into the desiredcrystalline form. The same result is achieved when a solvent suitablefor the purpose is used to purify the crude quinacridone; during theprocess of purification the solvent converts the quinacridone into thedesired crystalline form.

Thus when a quinacridone solution, as obtained after ring closure ofdiphenylaminoterephthalic acid with polyphosphoric acid, is poured intowater, for example, the quinacridone is obtained in the a crystal phase.If however the polyphosphoric acid solution containing the quinacridoneis carefully diluted with water while still hot, a mixture of the a and[3 crystal phases with the latter phase predominant is produced. Again,the crude quinacridone may be purified by heating with dimethylsulfoxideto give the 5 crystal phase, whereas if the purification is carried outby dissolving in dimethylsulfoxide containing alcoholic potassiumhydroxide solution and carefully precipitating by the addition of water,the quinacridone is obtained in the 7 crystal phase.

A number of the quinacridone dyestuffs obtainable according to thepresent process are new, namely those having the formula H 0 i ti n /1315 B A3 9 7 5 s C 6 I 4 in which at least one of the nuclei A and Bcontains a substituent of the groups halogen atoms, nitro groups, lowmolecular alkyl or alkoxy groups, and in which each of the nuclei A andB-when they are identical and contain only one type ofsubstituent-contain at least one nitro group, at least two low molecularalkyl groups, at least two low molecular alkoxy groups or at least threehalogen atoms, and in which not more than two low molecular alkyl oralkoxy groups are in the positions 1, 4, 8 and 11.

After suitable processing, the orange to blue quinacridones obtainedaccording to the present process can be employed for the coloration ofplastics, in particular polyvinyl chloride, of aqueous dispersions ofsynthetic resins for paints, of printing inks, of lacquers, of spinningsolutions of viscose rayon, cellulose 2 /2-acetate of cellulosetriacetate, of rubber, of high-quality papers, and for the pigmentprinting of textile fabrics. Certain members are also suitable for themass dyeing of polypropylene, synthetic polyamides (e.g. Perlon,registered trademark) and polyesters (e.g. Terylene, registeredtrademark).

The colors produced in paints, lacquers, synethic resin dispersions andpolyvinyl chloride, the spin dyeings of viscose and acetate fibers, andthe textile prints are characterized, besides their good all-roundfastness propare boiled in a flask equipped with a reflux condenser for5 /2 hours at 120-125 in presence of 2.5 parts of potassium iodide and0.2 part of anhydrous copper acetate. The reaction product is dilutedwith water, precipitated by the addition of hydrochloric acid, andpurified by redissolving in a dilute aqueous solution of ammonium orsodium hydroxide. By acidification of the solution with acetic acid, the2,5-diphenylaminoterephthalic acid is crystallized out and filtered off.On further acidification of the mother liquor with a mineral acid, e.g.hydrochloric acid, the 2-chloro-5-phenylarninoterephthalic acid isprecipitated.

2,5-dichloroterephthalic acid can be replaced by another2,5-dihalogenoterephthalic acid, e.g. 2,5-difiuoroterephthalic acid,2,5-dibromoterephthalic acid or 2,5- diiodoterephthalic acid or by amixed dihalogenoterephthalic acid, e.g. 2-chloro-S-fluoroterephthalicacid.

The anhydrous potassium carbonate may be replaced by the equivalentquantity of anhydrous sodium carbonate, sodium or potassium bicarbonate,dessicated borax, dessicated disodium or dipotassium phosphate ordessicated mixtures of monosodium/disodium phosphate ormonopotassium/dipotassium phosphate.

The dicondensation product 2,5-diphenylaminoterephthalic acid can alsobe obtained by the following procedure.

11.7 parts of sodium 2-chloro-S-phenylarninoterephthalate, obtainable asdescribed in Example 6, are dissolved at pH 7.5 in 250 parts of water ina vessel equipped with a stirring device and reflux condenser. Thesolution is heated to 95-98; first 9.5 parts of butyric acid (d.=0.947)are added, then dropwise 35 parts of aminobenzene and afterwards 2 partsof potassium fluoride and 0.2 part of copper acetate.

The mixture is then boiled for 24 hours with stirring and the productprocessed further as described above.

The 2-chloro-5-phenylaminoterephthalic acid can also be replaced by anequivalent amount of 2-bromo-5- phenylaminoterephthalic acid.

The solvent mixture of ethylene glycol and water can also be replaced byother polar solvents, e.g. water, ethylene glycol, propylene glycol,glycerine, polyethylene glycol, and low molecular alcohols, or a mixtureof water and glycerine.

The copper acetate may be replaced by the same quantity of cupricsulfate, chloride, benzoate, hydroxide or oxide, by cuprous chloride oroxide or by Raney copper.

In place of aminobenzene, substituted aromatic amines can be used inwhich case the corresponding substituted diarylaminoterephthalic acidsare obtained.

Ring closure giving quinacridone takes place when 2 parts ofdiphenylaminoterephthalic acid and 30 parts erties, by brightness ofshades and very good to outstanding fastness to light.

Especially notable features are the outstanding fastness to top finishesof paints and lacquers and, the excellent fastness to migration ofpolyvinyl chloride colored with the dyestuffs, and the good to very goodcolor fastness I 11.8 parts of 2,5-dichloroterephthalic acid, 15 partsof anhydrous potassium carbonate, 55 parts of ethylene glycol,

12.5 parts of water, and

76 parts of aminobenzene of polyphosphoric acid with a P 0 content ofare heated for 15 minutes at l55l60. The end product,quinacridine-7,14-dione, is precipitated by diluting the polyphosphoricacid with water at 80-100". The yield is very good and the slightlybluish red product is of high purity.

For carrying out ring closure, the ratio of diphenylaminoterephthalicacid to polyphosphoric acid can be varied within wide limits. When aratio of 1:5, for example, is chosen, the product is obtained in highyield.

7 X-ray photographs show that the product is a mixture of twocrystallographically ditferent quinacridones which are described inUnited States Patents 2,844,484 and 2,844,485. The greater proportion ofthe mixture is the product described in the second of these patents.

Depending on the conditions of the final operations, products ofdifferent crystal forms are obtained. For example, if 26 parts of thepolyphosphoric acid containing the quinacridone at 160 is run into 500parts of water at 20 stirred with a polytron stirrer, heated for 15minutes at 80, filtered off while hot and dried, a powder of an intensered to red-violet color is obtained which is identical with the productdescribed in US. Patent 2,844,484 and gives a red shade in polyvinylchloride. The 500 parts of water can be replaced by 500 parts of2-normal ammonia or 500 parts of 2-normal sodium hydroxide solution.

A product crystallographically the same is obtained when 1 part of theabove-described crude mixture is dissolved in parts of concentratedsulfuric acid or in a mixture of 30 parts of dimethyl sulfoxide and 3.5parts of 10% alcoholic potassium hydroxide solution, the solution runinto 200 or 400 parts of ice-Water and the whole boiled for 30 minutes,after which the precipitate formed is filtered off and dried.

A violet-colored quinacridone which is crystallographically differentfrom those previously described is obtained when 1 part of the mixtureproduced according to the present example is boiled with 25 parts ofdimethyl sulfoxide for 4 hours with refiux and allowed to stand in thissolvent for a further 84 hours. The product is isolated by dilution withwater. X-ray photography re veals it as identical With the productdescribed in US. Patent 2,844,485, its shade in polyvinyl chloride beingviolet.

Another modification is obtained when 1 part of the crude mixture isdissolved in a mixture of 32 parts of dimethyl sulfoxide and 3.6 partsof 10% alcoholic potassium hydroxide solution, the blue solutionfiltered free from impurities if necessary, and water added atapproximately 100 until precipitation starts, the pure pigment beingsubsequently filtered off at room temperature.

This modification is also obtained when 1 part of the crude quinacridonemixture is dissolved in a mixture of 50 parts of dimethyl formamide and2 parts of 10% alcoholic potassium hydroxide solution and water added tothe boiling solution until precipitation is initiated, upon which thepigment can be filtered off at room temperature.

The pure quinacridone, as it can be obtained by recrystallization frompolar solvents, e.g. dimethyl formamide, dimethyl sulfoxide, ethyleneglycol, or from mixtures of 10% alcoholic potassium hydroxide solutionand dimethyl formamide or dimethyl sulfoxide, or by recrystallizationfrom concentrated sulfuric acid, gives in concentrated sulfuric acidsolution at 20 in the visible region an absorption spectrum which ischaracterized by the positions of the following main absorption bands(Wave numbers in cm.- 16,650, 18,070, 19,420, 20,770 and 25,800. Theabsorption spectrum in concentrated sulfuric acid is independent of thedifferent forms revealed by X-ray photography.

The quinacridone mixture and the isolated modifications can be used forthe pigmentation of various substrates as state-d in the foregoingdescription of the process. The pigment colorations and the textileprints are outstandingly fast to light and migration.

EXAMPLE 2 11.8 parts of 2,5-dichloroterephthalic acid,

34.6 parts of anhydrous potassium carbonate,

220 parts of ethylene glycol,

50 parts of water,

50 parts of l-amino-2-methyl-4-chlorobenzene hydrochloride, and

5 parts of potassium iodide in the presence of 0.2 parts of anhydrouscopper acetate are boiled with reflux for 12 hours at 120-425". Thereaction product is processed further according to the particulars givenin Example 1. The product is 2,5-di-(2-methyl-4'-chlorophenylamino)terephthalic acid and 2 chloro 5(2'-methyl-4'-chloro)-phenylaminotereph thalic acid.

The excess amine can be blown out of the alkaline reaction medium withsteam, either before precipita- 6 tion with hydrochloric acid or aftercompletion of precipitation from the alkaline mother liquor.

The 1-amino-2-methyl-4-chlorobenzene hydrochloride can be replaced bythe free amine, in which case the amount of potassium carbonate must beproportionately reduced.

Ring closure resulting in the quinacri-done derivative can be carriedout by the method described in the seventh paragraph of Example 1. Oneobtains 2,9-dichloro-4,l1- dimethylquinacridine-7,14-dione as a redpowder.

The absorption spectrum in the visible region of the new quinacridonederivative in concentrated sulfuric acid at 21 is characterized by theposition of the following main absorption bands (wave numbers in cmr16,180, 17,570, 18,890 and 20,100.

After suitable processing, the2,9-dichloro-4,11-dimethylquinacridine-7,14-dione can be used forpigmenting various substrates of the types mentioned in the description.The pigment colorations and textile prints are outstandingly fast tomigration and very fast to light.

Polyvinyl chloride is colored a yellow-red.

EXAMPLE 3 are added and the temperature maintained at for a further 70hours. The reaction product is processed as described in Example 1 togive 2,5-di-(3-nitro-phenylamino)-terephthalic acid and 2 chloro5-(3-nitro)- phenylaminoterephthalic acid.

Ring closure to form the quinacridone derivative is conducted accordingto the method described in Example 1, paragraph 7, except that thetemperature is main tained at for 25 instead of only 15 minutes, and issubsequently increased and maintained at for a further 60 minutes.

The purified quinacridone derivative, which it is assumed to consistmainly of 3,10-dinitroquinacridine-7,14- dione, may also be 1,8- or1,10-dinitroquinacridine-7,14: dione or a mixture of the threesubstances.

Speaking generally, it may be said that ring closure of2,5-di-(3'-substituted)-arylamino terephthalic acids admits of threepossibilities for the formation of 3-quinacridine-7,l4-diones, namely3,10-, 1,8 :and 1,10-substituted quinacridine-7,14-diones, whilst withthe 2-arylamino 5-(3 substituted)-arylaminoterephthalic acids either 3-or l-substituted quinacridones may be formed.

The product of the present example yields red-violet colorations andtextile prints which are outstandingly fast to migration and very fastto light.

EXAMPLE 4 A further variation of the method of ring closure leading toformation of the quinacridone as described in Example 1, paragraph 7, isto replace the 2 parts of diphenylaminoterephthalic acid by 2 parts ofdiphenylaminoterephthalic acid diethyl ester. A bluish red powder 94.4parts of 2,5-dichloroterephthalic acid, 800 parts of ethylene glycol,

608 parts of aminobenzene, and

1.6 parts of copper acetate are heated at 140 for 8 hours.

The mass is treated further as described in Example 1 to form2,5-diphenylaminoterephthalic acid and 2 chloro--phenylaminoterephthalicacid. The latter can be purified by redissolving in dilute potassiumhydroxide solution and reprecipitating.

When 120 parts of anhydrous potassium acetate are added to the reactionmass of this example, and the mixture heated at 100 for 16 hours, theproportion of 2,5- diphenylaminoterephthalic acid in the end product canbe markedly increased. If one wishes to produce almost exclusively themonocondensation product, 2-chloro-5- phenylaminoterephthalic acid, theprocedure described in the next example is preferable.

EXAMPLE 6 A solution of 8.6 parts of crystallized copper sulfate in 40parts of water is added dropwise at 90-95 in 10-15 minutes with vigorousstirring to a solution of 7.05 parts of 2,5-dichloroterephthalic acidand 5.04 parts of sodium bicarbonate in 100 parts of water. Theprecipitated copper salt is filtered with suction at 8090 and washed. Itis suspended in a solution of 95 parts of water, 1 part of potassiumfluoride, 2.5 parts of anhydrous sodium acetate and 7.5 parts of aceticacid. The suspension is brought to the boil and 21 parts of aminobenzeneare added over the next minutes. After boiling for hours with reflux thesuspension is acidified at 70-80" with 30 parts of concentratedhydrochloric acid. The precipitated product is filtered with suction at20 and freed from any superficially attached aminobenzene by washingwith dilute hydrochloric acid. It is then suspended in 200* parts ofwater at 20, adjusted with sodium hydroxide to give a phenolphthaleinalkaline reaction, stirred for 2 hours and filtered. Acetic acid isadded to the solution at 7580 so that it reacts acid to litmus paper andis freed from any small amounts of dicondensation products which may bepresent. At the same temperature the solution is adjusted withhydrochloric acid to react weakly acid to Congo paper (pH 2-3) and theprecipitated monocondensation product is isolated. It is2-chloro-5-phenyl-aminoterephthalic acid and is obtained in good yield.

When the 2,5-dichloroterephthalic acid of the present example isreplaced by 2,5-dibromoterephthalic acid, a mixture of2-bromo-5-phenylaminoterephthalic acid and 2,5-diphenylaminoterephthalicacid is obtained in-which the ratio of 2,5-diphenylaminoterephthalicacid to 2- bromo-5-phenylaminoterephthalic acid is greater than When2,5-dichloroterephthalic acid is used as starting material.

16.8parts of the 2-chloro-S-phenylaminoterephthalic acid of thisexample,

200 parts of ethylene glycol,

3.75 parts of anhydrous potassium carbonate,

15 parts of anhydrous potassium acetate,

2.9 parts of potassium fluoride,

42.5 parts of 1-amino-2-methyl-4-chlorobenzene, and

0.2 part of copper acetate are heated for 16 hours at 140. The reactionmass is diluted with water, the product precipitated by acidificationwith hydrochloric acid, purified by dissolving in dilute ammoniasolution, and precipitated by acidifying the solution with acetic acid.

One can also arrive at Z-phenylamino-S-(2'-rnethyl-4-chloro)-phenylaminoterephthalic acid by condensing a 2-halogeno-S-(2"methyl-4-chloro)-phenylaminoterephthalic acid, e.g.2-chloro-5-(2'-methyl-4'-chloro)-phenyl-aminoterephthalic acid (Example2) with aminobenzene.

Ring closure giving the quinacridone is carried out in the Way describedin Example 1, paragraph 7. The precipitated crude2-chloro-4-methylquinacridone-7,14- dione is best purified byredissolving in concentrated sulfuric acid or in a mixture of dimethylsulfoxide and a1- coholic potassium hydroxide solution, followed byprecipitation with Water as described in Example 1. Alter- 8 natively,it can be recrystallized in polar solvents, e.g. dimethyl formamide orethylene glycol.

In the visible region of the spectrum the absorption of the purified2-chloro-4-methylquinacridine-7,14-dione in concentrated sulfuric acidat 21 is characterized by the positions of the following main absorptionbands (Wave numbers in cm.- 16,500, 17,900, 19,200, 20,500, 25,600. Thered dyeings, colorations and prints obtained with the2-chloro-4-methylquinacridine-7,14- dione are outstandingly fast tomigration and very fast to light.

EXAMPLE 7 16.8 parts of 2-chloro-5-phenylaminoterephthalic acid,produced by the methods described in Examples 1, 5 or 6,

200 parts of ethylene glycol,

3.75 parts of anhydrous potassium carbonate,

48.6 parts of 1-amino-3,4-dichlorobenzene,

2.9 parts of potassium fluoride,

15.0 parts of anhydrous potassium acetate, and

0.2 parts of copper acetate are heated for 16 hours at 140. The2-phenylamino-5- (3',4'-dichlo-ro)-phenylaminoterephthalic acid isprocessed further according to the details of Example 1, and ringclosure is carried out by the method of Example 1, paragraph 7, to givethe quinacridone. On purification a 2,3-dichloroquinacridine-7,14-dioneor a 1,2-dichloroquinacridine-7,14-dione or a mixture of the two isobtained. The absorption spectrum of the reaction product inconcentrated sulfuric acid at 21 is characterized in the visible regionby the positions of the following main absorption bands (wave numbers incm. 16,500, 17,900, 19,250, 20,600.

The violet-red colorations and prints produced with the quinacridone areoutstandingly fast to migration and very fast to light.

EXAMPLE 8 Amixture of 8.1 parts of 2,5-dibromoterephthalic acid, partsof water,

parts of methanol,

3.7 parts of anhydrous potassium carbonate, 5.0 parts of anhydrouspotassium acetate, 12.3 parts of 1-amino-3-methoxybenzene, 12.8 parts of1-amion-2-chlorobenzene, and 0.4 part of copper acetate are boiled withreflux for 16 hours at 70 and further processed on the lines ofExample 1. The method of ring closure is also as described in paragraph7 of Example 1. The red colorations and prints produced with theproducts are outstandingly fast to migration and have very good lightfastness.

With another low molecular alcohol (ethanol, n-propanol, isopropanol orbutanol) similar results are obtained.

EXAMPLE 9 5 parts of 2,S-diphenylaminoterephthalic acid diethyl esterare heated with parts of 78.5% sulfuric acid for 15 minutes at 205,allowed to cool and then run into water. The precipitated quinacridoneis purified by one of the methods described in Example 1.

A similar result is obtained when 5 parts of the ester are mixed with 25parts of boric acid, heated first to 120, and then to 320, maintainedfor 1 hour at 320 and run into water.

The 2,S-diphenylaminoterephthalic acid diethyl ester of this example canbe replaced by an equal quantity of 2,5-diphenylarninoterephthalic acid.The sulfuric acid likewise can be replaced by a mixture of crystallizedboric acid and 78.5% sulfuric acid in the proportion of 1:10.

In the following table further examples are listed.

9. The quinacr-idine-7,14-di-ones are obtained by ring closare of a2,S-diarylaminoterephthalic acid of the formula:

which can also be employed in the form of its ester, they arecharacterized in the table by the nuclei A and B in columns (I) and (II)and by the shade of the colors produced in polyvinyl chloride with thepigment (column (III) I Table Exam A 1 11 1B 11 1 time? 1 l I r ra 'cayvmy ple No Aryl radica A chloride (In) Z-nitro hen l.- Z-nitrophenyl.Red. it Phenyiinjlhn; 2-methylphenyl Do. 3 methylpheny D0.Z-methoxyphenyl V iolet-red. 3-methoxyphenyl Red. A-methoxyphenylViolet-blue. 2-chlorophenyl. Yellow-red. 3-chlorophenyl Red.4-ehloz'ophenyl Violet-red. 3 ethylphenyl Red. 3-etl1oxyphenyL- o.2-fiuorophcny Yellow-red. 2-br0mophenyl 0.

S-fl uorophenyl 3-bromophenyl- 4-fiuorophenyl t-bromopl'lenyl2,4'diehl0ropl1enyL 2, -dich lorophenyL 0. 3.4-diehlorophonyl-Violetred.

Rod.

2,3-dichlorophenyl- 2,4,5-trichlorophenyl. D0. Z-nitrophenyl Violet-red.3-nitrophenyl. Red. 34 d0 4-methylphenyl Violet-red 35 Z-methylphenyl...B-methylphenyL ed.

3-n1ethylphenyl 4-ethylpheny1 Do. 2-methylphenyl 3-methoxypheny Do.4-methylphenyl... 2,4-d1methylphen Violet-red 2-methoxyphen1y1"3-merhoxypheny1 adj)O -ethox hen 0 h lqneth igzphe hyL2,4-dimethoxy-phenyl Violet. 2-ehlorophenyl. 3-ohlorophenyl Yellow-red.do 2-b1'omopnenyl Do,

2,4-clichlorophen ed. 2,5-dichl0rophenyL Yellow-red 3,4 dlchl0rophenyled. 2,3-diohlorophenyl D0. 2,5-dioromophenyL- Yellow-red do2A=-dibromophenyl Red. 50 -I 2,3-dichloro- 2,4-dichlorophenyl Do.

henyl. 51 2,35-trichloro- 2,4,5-trichlorophenyl D0.

phenyl.

Having thus disclosed the invention what we claim 1s:

1. 4,1 1-dinitroquinacridine-7, l4-dione.

2. 2 phenylamino 5 (2-methyl-4'-chloro)-phenylaminoterephthalic acid. v

3. 2-phenylamino 5 (3,4-dichloro)-phenylam1noterephthalic acid.

4. 2 (3-methoxy)-phenylamino-5-(2-chloro)-phenylaminoterephthalic acid.

5. Z-phenylamino 5 (3' halogeno) phenylamlno terephthalic acid.

6. Z-phenylamino 5 (4' halogeno) phenylammo terephthalic acid.

7. Z-phenylamino 5 (2' halogeno) phenylamlno terephthalic acid.

8. 2-phenylamino 5 (3' methoxy) phenylammo terephthalic acid.

9. 2,5-di-(2'-nitro)-phenylamino terephthalic acid.

10. Symmetrical quinacridine-7,14-dione of the formula:

19 wherein the symbols X'represent nitro groups.

11. In the preparation of di-arylamino-terephthalic acid compound, theimprovement which consists essentially of (I) reacting, at a temperaturebetween 70 and C. and with a pH range of from 2 to 12 in contact with(A) copper catalyst, (B) acid-binding agent, and (C) polar solventselected from the group consisting of water, low molecular alcohol offrom 1 to 4 carbon atoms, glycerine, ethylene glycol, propylene glycoland polyethylene glycol, (1) one mole of a member selected from thegroup consisting of a 2,S-dihalogenoterephthalic acid and a 2,5-dihalogenoterephthalic acid ester with (2) one mole of a monocycliccarbocyclic aromatic amine, wherein from 1 to 2 of the positions orthoto the amino group are free, whereby a monohalogeno monoarylaminoterephthalic acid compound is obtained, and (II) reacting, at atemperature between 70 and 160 C. and within a pH range of from 2 to 12in contact with (A) copper catalyst, (B) acid-binding agent and (C)polar solvent selected from the group consisting of water, low molecularalcohol of from 1 to 4 carbon atoms, glycerine, ethylene glycol,propylene glycol and polyethylene glycol, (3) one mole of saidmonohalogeno-monoarylamino-terephthalic acid compound with (4) one moleof a member selected from the group consisting of (a) the same aromaticamine as employed in step I, (12) another monocyclic carbocyclicaromatic amine wherein from 1 to 2 of the positions ortho to the aminogroup are free, and (c) a mixture of said aromatic amines.

12. A process which consists essentially of reacting, at a temperaturebetween 70 and 160 C. and within a pH range of from 2 to 12 in contactwith (1) copper catalyst, (2) acid-binding agent, and (3) polar solventselected from the group consisting of water, low molecular alcohol offrom 1 to 4 carbon atoms, glycerine, ethylene glycol, propylene glycoland polyethylene glycol, one mole of a member selected from the groupconsisting of a 2,5-dihalogenoterephthalic acid and a2,5dihalogenoterephthalic acid ester with a member selected from thegroup consisting of (a) two moles of a monocyclic carbocycli c aromaticamine, wherein from 1 to 2 of the positions ortho to the amino group arefree, (b) one mole of one monocyclic aromatic amine of the benzeneseries and one mole of another monocyclic aromatic amine of the benzeneseries, from 1 to 2 of the positions ortho to the amino group in each ofsaid amines being free, and (0) two moles of a mixture of monocycliccarbocyclic aromatic amines, from 1 to 2 of the positions ortho to theamino group in each of said amines being free.

13. In the preparation of di-arylamino-terephthalic acid compounds, theimprovement which consists essentially of (I) reacting, at a temperaturebetween 70 and 160 C. and within a pH range of from 2 to 12 in contactwith (A) finely divided metallic copper catalyst, (B) acid-bindingagent, and (C) polar solvent selected from the group consisting ofwater, low molecular alcohol of from 1 to 4 carbon atoms, glycerine,ethylene glycol, propylene glycol and polyethylene glycol, (1) one moleof a member selected from the group consisting of a 2,5-dihalogenoterephthalic acid and a 2,5-dihalogenoterephthalic acid esterwith (2) one mole of a monocyclic carbocyclic aromatic amine, whereinfrom 1 to 2 of the positions ortho to the amino group are free, wherebya mono.- halogeno-monoarylamino-terephthalic acid compound is obtained,and (II) reacting, at a temperature between 70 and 160 C. and within apH range of from 2 to 12 in contact with (A) copper catalyst, (B)acid-binding agent, and (C) polar solvent selected from the groupconsisting of water, low molecular alcohol of from 1 to 4 carbon atoms,glycerine, ethylene glycol, propylene glycol and polyethylene glycol,(3) one mole of said monohalogeno-monoarylamino-terephthalic acidcompound with (4) one mole of a member selected from the groupconsisting of (a) the same aromatic amine as employed I 1' 12 in step I,(12) another monocyclic carbocyclic aromatic OTHER REFERENCES amincwhemin from 1 to 2 of thfiPositions oftho to h Borckmann et a1.: Ber.Deut. Chem., volume 89, pages arnrno group are free and (c) a rmxture ofsa1d aromatlc 13794397 (1956) pages 1392, 1396 and 1397 apply. ammes-Lemstedt et a1.: Ber. der Deut. Chem., volume 70, page 5 1526 (1937).References Cited by the Examiner Lesnianski et a1.: Roczniki Chemji,volume 6, page 890,

UNITED STATES PATENTS 1926. 2,342,885 2/44 Morgan Liebermann: Annalen,volume 518 (1935), pages 245- 2,694,713 11/54 Brody 260279 260, Pages245-6 relied 2,726,920 12/55 Federkial et 3 4 10 Organic Synthesis,volume pages 2 740 7 4 56 Ham 8 4 T11R16! J.A.C.S., volume 45, page 1906(1923).

2 21 529 1 5 Struve 2 0 279 Wilkinson 8t 8.1.1 J. Chem. SOC. (London),1948, pages 2,821,530 1/58 Struve 260279 (P 35 relied 2,330,990 4/58Struve 26O 279 Uhllg: Angewandte Chemie, volume 66, pages 435- 2,s44,4s57/58 Struve 260 279 15 436 2,906,590 9/59 Evans 862 NICHOLAS S. RIZZO,Primary Examiner.

FOREIGN P A TENTS IRVING MARCUS, HERBERT J. LIDOFF, WALTER 602,334 5/48Great Bntaln. A MODANCE, Examiners.

9. 2,5-DI-(2''-NITRO)-PHENYLAMINO TEREPHTHALIC ACID.
 10. SYMMETRICALQUINACRIDINE-7,14-DIONE OF THE FORMULA:
 11. IN THE PREPARATION OFDI-ARYLAMINO-TEREPHTHALIC ACID COMPOUND, THE IMPROVEMENT WHICH CONSISTSESSENTIALLY OF (I) REACTING, AT A TEMPERATURE BETWEEN 70* AND 160*C. ANDWITH A PH RANGE OF FROM 2 TO 12 IN CONTACT WITH (A) COPPER CATALYST, (B)ACID-BINDING AGENT, AND (C) POLAR SOLVENT SELECTED FROM THE GROUPCONSISTING OF WATER, LOW MOLECULAR ALCOHOL OF FROM 1 TO 4 CARBON ATOMS,GLYCERINE, ETHYLENE GLYCOL, PROPYLENE GLYCOL AND POLYETHYLENE GLYCOL,(1) ONE MOLE OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF A2,5-DIHALOGENOTEREPHTHALIC ACID AND A 2,5DIHALOGENOTEREPHTHALIC ACIDESTER WITH (2) ONE MOLE OF A MONOCYCLIC CARBOCYCLIC AROMATIC AMINE,WHEREIN FROM 1 TO 2 OF THE POSITIONS ORTHO TO THE AMINO GROUP ARE FREE,WHEREBY A MONOHALOGENO-MONOARYLAMINO-TEREPHTHALIC ACID COMPOUND ISOBTAINED, AND (II) REACTING, AT A TEMPERATURE BETWEEN 70* AND 160*C. ANDWITHIN A PH RANGE OF FROM 2 TO 12 IN CONTACT WITH (A) COPPER CATALYST,(B) ACID-BINDING AGENT AND (C) POLAR SOLVENT SELECTED FROM THE GROUPCONSISTING OF WATER, LOW MOLECULAR ALCOHOL OF FROM 1 TO 4 CARBON ATOMS,GLYCERINE, ETHYLENE GLYCOL, PROPYLENE GLYCOL AND POLYETHYLENE GLYCOL,(3) ONE MOLE OF SAID MONOHALOGENO-MONOARYLAMINO-TEREPHTHALIC ACIDCOMPOUND WITH (4) ONE MOLE OF A MEMBER SELECTED FROM THE GROUPCONSISTING OF (A) THE SAME AROMATIC AMINE AS EMPLOYED IN STEP I, (B)ANOTHER MONOCYCLIC CARBOCYCLIC AROMATIC AMINE WHEREIN FROM 1 TO 2 OF THEPOSITIONS ORTHO TO THE AMINO GROUP ARE FREE, AND (C) A MIXTURE OF SAIDAROMATIC AMINES.